Methods of making polymer blend compositions

ABSTRACT

Methods of making miscible and compatible immiscible polymer blends are disclosed. The polymer blends have a polyimide as a component. The miscible polymer blends have a single glass transition temperature. The compatible polymer blends have two glass transition temperatures.

BACKGROUND OF THE INVENTION

Compositions having a polymer blend and methods of making them aredisclosed herein.

Polymer blends are widely employed in a range of applications. Forexample, substitution of metal parts with parts made from plasticmaterials (polymer compositions) results in parts having lighter weightand similar or improved performance properties. In many applications,such as parts used under an automobile hood, plastic materials with ahigh heat resistance are required. Frequently though, plastic materialshaving a high heat resistance are difficult to mold. Blending polymersis one approach to achieving a plastic material with a desired set ofphysical properties such as high heat resistance and processability.Polymer blends may comprise miscible polymers, immiscible polymers, or acombination of miscible and immiscible polymers. Blends comprisingimmiscible polymers have two or more phases and such blends may becompatible or incompatible. Incompatible blends of immiscible polymerscan suffer from phase separation as demonstrated by delamination or theformation of skin-core layered structures during polymer processingoperations, especially injection molding. The term, “delamination,” asused when referring to such materials, describes visually observedseparation of a surface layer giving a flaking or onion skin effect.Incompatibility may also result in poor mechanical properties andmarginal surface appearance (streaking, pearlescence, etc.). Compatibleblends of immiscible polymers typically do not show any delamination andcan result in acceptable end-use properties.

Miscible polymer blends, on the other hand, may offer desirable end-useproperties and the advantage of tailoring product propertiesintermediate of the individual components across the misciblecomposition range. Miscible blends do not suffer from delamination andgenerally have consistent physical properties.

So while a miscible blend of two polymers is generally desirable it canbe difficult to achieve. Blends of two polymers of a same or similarclass might be expected to have a better chance of miscibility. However,polymers from the same class are frequently immiscible and formmultiphasic compositions. For example, ACUDEL 2000 from Solvay is animmiscible blend of two polysulfones—PPSU and PSU. In addition, manysuch examples of immiscible blends of polymers in the same class existin the literature. Thus, polymer miscibility is difficult to predict,even within the same class of polymers.

For the foregoing reasons there remains an unmet need fornon-delaminated polymer blends, i.e., blends free of delamination, whichare either miscible blends or immiscible, but nonetheless compatible,blends. More particularly, there remains an unmet need to develop blendshaving high heat resistance, and methods of forming such polymer blends.

BRIEF DESCRIPTION OF THE INVENTION

The invention includes methods of making thermoplastic compositionscomprising a non-delaminated polymer blend. In one embodiment a methodof making a polymer blend comprises melt mixing a pre-polymer and apolymer. The pre-polymer has a component selected from the groupconsisting of free amine groups, free anhydride groups, and combinationsthereof; and comprises structural units derived from a dianhydride and adiamine. The polymer comprises a reactive member selected from the groupconsisting of structural groups, end groups, and combinations thereof.The reactive member is reactive with the free anhydride groups, the freeamine groups, or combinations thereof. The polymer blend isnon-delaminated.

In some embodiments the method comprises using a polymer comprisingstructural units derived from a dianhydride and a diamine. In someembodiments the pre-polymer and polymer employ a common diamine ordianhydride. When the pre-polymer and polymer employ a common diamine ordianydride the polymer blend may have a predetermined glass transitiontemperature, provided that the pre-polymer and polymer are present inamounts sufficient to provide a blend having the selected glasstransition temperature.

In some embodiments the method comprises using a pre-polymer and apolymer derived from different diamines and dianhydrides. When thepre-polymer and polymer are derived from different diamines anddianhydrides the polymer blend may have more than one predeterminedglass transition temperature.

In some embodiments a method of making a composition comprises forming apolymer blend by melt mixing a pre-polymer and a polymer and then meltmixing the polymer blend with an additional component. The pre-polymercomprises a component selected from the group consisting of free aminegroups, free anhydride groups, and combinations thereof and comprisingstructural units derived from a dianhydride and a diamine. The polymercomprises a reactive member selected from the group consisting ofstructural groups, end groups, and combinations thereof. The reactivemember is reactive with the free anhydride groups, the free aminegroups, or combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a photograph of a sample showing delamination.

FIG. 2 is a photograph of a sample essentially free from delamination.

DETAILED DESCRIPTION OF THE INVENTION

The invention is based on the unexpected discovery that it is nowpossible to form non-delaminated compositions that are derived from (a)pre-polymers having free amine groups and/or free anhydride groups and(b) a polymers having structural groups and/or end groups that arereactive with the pre-polymer's free anhydride groups and/or free aminegroups. Surprisingly, the compositions (and articles derived from thecompositions) can overcome the problem of delamination typically foundin immiscible, incompatible blends. Compositions (and articles derivedfrom the compositions) can also exhibit improved miscibility andincrease the range of miscible blend compositions.

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, and the like, used in the specification and claims are to beunderstood as modified in all instances by the term “about.” Variousnumerical ranges are disclosed in this patent application. Because theseranges are continuous, they include every value between the minimum andmaximum values. Unless expressly indicated otherwise, the variousnumerical ranges specified in this application are approximations.

The terms “first,” “second,” and the like, “primary,” “secondary,” andthe like, “(a),” “(b)” and the like, as used herein do not denote anyorder, quantity, or importance, but rather are used to distinguish oneelement from another. The terms “a” and “an” do not denote a limitationof quantity, but rather denote the presence of at least one of thereferenced item. “Optional” or “optionally” means that the subsequentlydescribed event or circumstance may or may not occur, and that thedescription includes instances where the event occurs and instanceswhere it does not. The endpoints of all ranges directed to the samecomponent or property are inclusive of the endpoint and independentlycombinable. Reference throughout the specification to “one embodiment,”“another embodiment,” “an embodiment,” “some embodiments,” and so forth,means that a particular element (e.g., feature, structure, property,and/or characteristic) described in connection with the embodiment isincluded in at least one embodiment described herein, and may or may notbe present in other embodiments. In addition, it is to be understoodthat the described element(s) may be combined in any suitable manner inthe various embodiments.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

The definition of benzylic proton is well known in the art, and as usedherein it encompasses at least one aliphatic carbon atom chemicallybonded directly to at least one aromatic ring, such as a phenyl orbenzene ring, wherein said aliphatic carbon atom additionally has atleast one proton directly bonded to it.

As used herein “substantially free of benzylic protons” or “essentiallyfree of benzylic protons” means that the pre-polymer, such as forexample a polyimide sulfone pre-polymer, has less than about 5 mole % ofstructural units, in some embodiments less than about 3 mole %structural units, and in other embodiments less than about 1 mole %structural units derived containing benzylic protons. “Free of benzylicprotons,” which are also known as benzylic hydrogens, means that thepre-polymer contains zero mole % of structural units derived frommonomers and end cappers containing benzylic protons or benzylichydrogens. The amount of benzylic protons can be determined by ordinarychemical analysis based on the chemical structure. In one embodiment thepolymer blend is essentially free of benzylic protons.

The term “alkyl” is intended to include both C₁₋₃₀ branched andstraight-chain, unsaturated aliphatic hydrocarbon groups having thespecified number of carbon atoms. Examples of alkyl include, but are notlimited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl,t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n-and s-heptyl, and, n- ands-octyl. The term “aryl” is intended to mean an aromatic moietycontaining the specified number of carbon atoms, such as, but notlimited to phenyl, tropone, indanyl or naphthyl.

All ASTM tests are based on the 2003 edition of the Annual Book of ASTMStandards unless otherwise indicated.

The term “polymer blend” as used herein means a macroscopicallyhomogeneous mixture of two or more different polymers. The term“miscible blend” describes a polymer blend having a single glasstransition temperature (T_(g)) and a monophasic resin morphology asdetermined by transmission electron microscopy at a magnification offifteen thousand (15,000). “Delamination” describes the separation of asurface layer from the body of an article molded from a polymercomposition. The presence or absence of delamiration can be determinedby visual inspection (20/20 vision) at a distance of one half (½) meteras described in greater detail below.

A “compatible” polymer blend is an immiscible polymer blend thatexhibits macroscopically uniform physical properties throughout itswhole volume, has more than one glass transition temperature (T_(g)),and shows multiphasic resin morphologies when viewed by electronmicroscopy as described above, but shows no delamination.

The term “non-delaminated” refers to the property of a composition or anarticle derived from the composition, in which the article or thecomposition does not exhibit visually observed separation of a surfacelayer showing a flaking or onion skin effect. A non-delaminated articlemay also be referred to herein as “essentially free from delamination.”

“Essentially free from delamination” is defined as showing nodelamination by visual inspection. In one embodiment, the specimen usedfor inspection is an injection molded bar. A specimen showingdelamination is shown in FIG. 1. A specimen essentially free fromdelamination is shown in FIG. 2. “Visual inspection” is determined byunaided vision (e.g., 20/20 vision in the absence of any magnifyingdevice with the exception of corrective lenses necessary for normaleyesight) at a distance of one half (½) meter.

The “pre-polymer” is an incompletely imidized oligomer comprisingstructural units derived from a dianhydride and a diamine. Exemplarydianhydrides have the formula (I)

wherein V is a tetravalent linker selected from the group consisting ofsubstituted or unsubstituted, saturated, unsaturated or aromaticmonocyclic and polycyclic groups having 5 to 50 carbon atoms,substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms,substituted or unsubstituted alkenyl groups having 2 to 30 carbon atomsand combinations comprising at least one of the foregoing linkers.Suitable substitutions and/or linkers include, but are not limited to,carbocyclic groups, aryl groups, ethers, sulfones, sulfides amides,esters, and combinations comprising at least one of the foregoing.Exemplary linkers include, but are not limited to, tetravalent aromaticradicals of formula (II), such as:

wherein W is a divalent moiety such as —O—, —S—, —C(O)—, —SO₂—, —SO—,—C_(y)H_(2y) (y being an integer of 1 to 20), and halogenatedderivatives thereof, including perfluoroalkylene groups, or a group ofthe formula —O-Z-O— wherein the divalent bonds of the —O— or the —O-Z-O—group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Zincludes, but is not limited to, divalent moieties of formula (III).

wherein Q includes, but is not limited to, a divalent moiety comprising—O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— (y being an integer from 1to 20), and halogenated derivatives thereof, including perfluoroalkylenegroups. In some embodiments the tetravalent linker V is free ofhalogens. In some embodiments groups free of benzylic protons are usedas the resulting pre-polymer (as well as the polymer blend) can havesuperior melt stability.

In one embodiment, the dianhydride comprises an aromatic bis(etheranhydride). Examples of specific aromatic bis(ether anhydride)s aredisclosed, for example, in U.S. Pat. Nos. 3,972,902 and 4,455,410.Illustrative examples of aromatic bis(ether anhydride)s include:2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (bisphenol-Adianhydride); 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propanedianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylether dianhydride;4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfidedianhydride;4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenonedianhydride and4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfonedianhydride, as well as mixtures comprising at least two of theforegoing. In one embodiment the dianhydride is selected from the groupconsisting of oxydiphthalic anhydrides, bisphenol-A dianhydrides andcombinations thereof.

The bis(ether anhydride)s can be prepared by the hydrolysis, followed bydehydration, of the reaction product of a nitro substituted phenyldinitrile with a metal salt of dihydric phenol compound in the presenceof a dipolar, aprotic solvent.

A chemical equivalent to a dianhydride may also be used. Examples ofdianhydride chemical equivalents include tetra-functional carboxylicacids capable of forming a dianhydride and ester or partial esterderivatives of the tetra functional carboxylic acids. Mixed anhydrideacids or anhydride esters may also be used as an equivalent to thedianhydride. As used throughout the specification and claims“dianhydride” will refer to dianhydrides and their chemical equivalents.

Useful diamines have the formula:

H₂N—R¹⁰—NH₂   (IV)

wherein R¹⁰ is a substituted or unsubstituted divalent organic moietysuch as: an aromatic hydrocarbon moiety having 6 to 20 carbons andhalogenated derivatives thereof; straight or branched chain alkylenemoiety having 2 to 20 carbons; cycloalkylene moiety having 3 to 20carbon atom; or divalent moieties of the general formula (V)

wherein Q is defined as above. Examples of specific organic diamines aredisclosed, for example, in U.S. Pat. Nos. 3,972,902 and 4,455,410.Exemplary diamines include ethylenediamine, propylenediamine,trimethylenediamine, diethylenetriamine, triethylenetertramine,hexamethylenediamine, heptamethylenediamine, octamethylenediamine,nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine,1,18-octadecanediamine, 3-methylheptamethylenediamine,4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine,5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine,2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine,N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine,1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide,1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane,m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene,2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine,2-methyl-4,6-diethyl-1,3-phenylene-diamine,5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene,bis(4-aminophenyl)methane,bis(2-chloro-4-amino-3,5-diethylphenyl)methane,bis(4-aminophenyl)propane, 2,4-bis(p-amino-t-butyl)toluene,bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene,bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene,bis(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfone,bis(4-aminophenyl)ether and 1,3-bis(3-aminopropyl)tetramethyldisiloxane.Mixtures of these compounds may also be used. In one embodiment thediamine is an aromatic diamine, or, more specifically,m-phenylenediamine, p-phenylenediamine, sulfonyl dianiline and mixturesthereof. In one embodiment the diamine is selected from the groupconsisting of diamino diaryl sulfones, metaphenylene diamines,paraphenylene diamines, and combinations thereof.

In some embodiments the pre-polymer is a polyetherimide pre-polymercomprising structural units derived from oxydiphthalic anhydride (ODPA)and diamino diaryl sulfone (DAS). Oxydiphthalic anhydride has thegeneral formula (VI):

and derivatives thereof as further defined below.

The oxydiphthalic anhydrides of formula (VI) includes4,4′-oxybisphthalic anhydride, 3,4′-oxybisphthalic anhydride,3,3′-oxybisphthalic anhydride, and any mixtures thereof. For example,the oxydiphthalic anhydride of formula (VI) may be 4,4′-oxybisphthalicanhydride having the following formula (VII):

The term oxydiphthalic anhydrides includes derivatives of oxydiphthalicanhydrides which may also be used to make the pre-polymer. Examples ofoxydiphthalic anhydride derivatives which can function as a chemicalequivalent for the oxydiphthalic anhydride in polyetherimide formingreactions include oxydiphthalic anhydride derivatives of the formula(VIII)

wherein R¹ and R² of formula VIII can be, independently at eachoccurrence, any of the following: hydrogen; a C₁-C₈ alkyl group; an arylgroup. R¹ and R² can be the same or different to produce anoxydiphthalic anhydride acid, an oxydiphthalic anhydride ester, and anoxydiphthalic anhydride acid ester.

Derivatives of oxydiphthalic anhydrides may also be of the followingformula (IX):

wherein R¹, R², R³, and R⁴ of formula (IX) can be, independently at eachoccurrence, any of the following: hydrogen; a C₁-C₈ alkyl group, an arylgroup. R¹, R², R³, and R⁴ can be the same or different to produce anoxydiphthalic acid, an oxydiphthalic ester, and an oxydiphthalic acidester.

Diamino diaryl sulfones (DAS) have the general formula (X):

H₂N—Ar¹—SO₂—Ar²—NH₂   (X)

wherein Ar¹ and Ar² independently are an aryl group containing a singleor multiple rings. Several aryl rings may be linked together, forexample through ether linkages, sulfone linkages or more than onesulfone linkages. The aryl rings may also be fused. In one embodimentAr¹ and Ar² independently comprise 5 to 12 carbons. In one embodimentAr¹ and Ar² are both phenyl groups.

In one embodiment, the pre-polymer is an ODPA/DAS polyetherimidecomprising more than 1, specifically 10 to 1000, or, more specifically,30 to 500 structural units of formula (XI):

wherein Ar¹ and Ar² are defined as above.

In one embodiment, the pre-polymer has a total reactive end groupconcentration of 0.5 to 20 mole % resin. Reactive end groups are definedas anhydrides and their chemical equivalents and amines. In someembodiments, a pre-polymer has a weight average molecular weight of1,000 to 100,000 grams per mole (g/mole) as measured by gel permeationchromatography (GPC).

The pre-polymer can have different ratios of carbon (C) atoms tonon-carbon atoms such as nitrogen (N), oxygen (O), and sulfur (S). Forinstance, in one embodiment, the pre-polymer can have a ratio of Catoms/N+O+S atoms of 2.8 to 4.2. In one embodiment, the number of oxygenatoms is greater than or equal to 2.5 times the number of nitrogenatoms. In another embodiment, the number of oxygen atoms is 2.5 to 5.0times more than the number of nitrogen atoms. In another embodiment, thenumber of oxygen atoms is greater than or equal to 7 times the number ofsulfur atoms. In another embodiment, the number of oxygen atoms is 7 to10 times the number of sulfur atoms.

The pre-polymer may be made by any suitable process, such as the processdescribed in U.S. Pat. No. 4,835,249. In this method, reactant monomersare dissolved in a solvent and then polymerized to an extent where thepolymer precipitates from solution and can eventually be isolated byfiltration or other related separation technique.

When the pre-polymer is an ODPA/DAS pre-polymer the pre-polymer is madeusing a slurry/precipitation method comprising stirring a diamine and adianhydride in a solvent to form a slurry, heating the slurry to atemperature sufficient for the diamine and dianhydride to react whereinthe temperature is below the melting point of the dianhydride, below themelting point of the diamine, or below the melting points of thedianhydride and diamine, and reacting the diamine and dianhydride toform a polyetherimide having sufficient molecular weight to precipitatefrom the solvent.

In the above process, it is important that the reaction temperature iskept below the melting point of the minimally soluble monomers so thatthe polymers precipitate as fine powder from the slurry that is easilystirred. It can be useful to remove water, or other volatile by-productsfrom the reaction mixture by distillation or other means. In oneembodiment azeotropic distillation of water is employed. In someembodiments water can be removed by chemical absorption using, forexample, molecular sieves. In other instances water can be removed usinga stream of a gas, for example nitrogen, passing over or through thereaction mixture. In addition, a combination of two or more waterremoval methods may be employed.

In one embodiment, the polymerization is conducted entirely below themelting point of the minimally soluble monomer(s). This may be usefulwhen the boiling point temperature of the solvent and the melting pointof the minimally soluble monomer(s) are greater than 100° C., to allowremoval of water from the polymerization reaction at atmosphericpressure.

It can be useful to conduct the polymerization under pressure, forexample at 1 to 300 pounds per square inch (psi) (21.1 kilograms forceper square centimeter (kgf/cm²)), or, more specifically, 1 psi (0.070kgf/cm²) to 100 psi (7.0 kgf/cm²). This can be done for a variety ofreasons, one being to raise reaction temperature and increase the rateof imidization. In order to prevent sticking or clumping of theprecipitated polymer it is still important to maintain temperature belowthe melting point of the minimally soluble monomer(s) even when pressureis increased. In some embodiments, it may be useful to remove water fromthe reaction while pressure is maintained at atmospheric pressure. Insome embodiments it can be useful to remove water in a multi stepprocess employing pressures greater than or equal to atmosphericpressure.

After the consumption of equal to or greater than 50 weight percent(wt-%) of the initial charge of the monomers it can be useful in someembodiments to isolate the precipitated polymer. In other embodimentsthe precipitated polymer may be isolated when equal to or greater than90 wt % of the initial charge of monomers are consumed. This can be doneusing a variety of methods, for example, filtration, centrifugation,floatation, freeze-drying, and combinations comprising one or more ofthe foregoing methods. In some embodiments equal to or greater than 95wt % of the isolated precipitated polyetherimide, based on the totalweight of the isolated precipitated polyetherimide, passes through a 2millimeter (mm) mesh screen. In some embodiments the isolatedprecipitated polyetherimide is a free flowing powder with an averageparticle size of 10 to 5000 micrometers.

The solvent used to form the slurry is chosen such that one or more ofthe initial monomers is minimally soluble. “Minimally soluble” isdefined as 1 to 50 wt % of the monomer is undissolved at the start ofthe reaction (at the initial reaction conditions). In addition, thesolvent should be chosen such that the resultant polymer is largelyinsoluble, that is to have a polymer solubility of less than or equal to10 wt %, or, even more specifically, less than or equal to 5 wt %, or,even more specifically, less than or equal to 1 wt %. In someembodiments the solvent comprises an aprotic polar solvent. In someembodiments, the solvent is insoluble in water, that is less than orequal to 5 wt %, or, more specifically, less than or equal to 1 wt %,based on the total amount of solvent, of the solvent dissolves in anequal amount of water at room temperature. In some embodiments, thesolvent has a high auto ignition temperature, for example greater thanor equal to 70° C., to reduce the potential fire hazard during theprocess and during any subsequent isolation.

In addition, a solvent free of nitrogen atoms, phosphorus atoms, sulfuratoms or a combination comprising two or more of the foregoing may beuseful in some embodiments. Solvents without these more polar atoms maybe easier to remove from the polymer and being less effective solventsare more likely to have monomers and polymers that are minimally solubleor insoluble.

Examples of useful solvents for forming the pre-polymer includehalogenated aromatics, such as chlorobenzene, dichlorobenzene,trichlorobenzene and bromobenzene; aryl ethers such as phenetole,anisole and veratrole; alkylaromatics such as xylenes and toluene; nitroaromatics such as nitrobenzene; polyaryl species such as naphthylene andalkyl substituted fused aromatic systems; aryl sulfone; high molecularweight alkane compounds such as mineral oils; and combinationscomprising one or more of the foregoing solvents. In some embodimentsthe solvent or combination of solvents has an atmospheric boiling pointof 150 to 250° C.

The reaction to form the pre-polymer may be run at any level ofreactants versus solvent. In some instances the weight % solids can be 5to 50% by weight of reactants to solvent at the start of thepolymerization reaction. In other instances, concentrations of 15 to 40%by weight may be useful. In still other instances higher concentrationsof reactants to solvent may be used to gain reactor efficiency.

Polyetherimide pre-polymer may be made using the precipitative processby reaction of more or less equal molar amounts of dianhydride (orchemical equivalent of a dianhydride) with a diamine. In someembodiments the amount of dianhydride and diamine differ by less than 5mole %; this helps to give polymers of sufficient molecular weight (Mw),for example greater than or equal to 1,000 g/mol, to precipitate fromthe reaction medium and have useful mechanical properties such asstiffness, impact strength and resistance to tearing or cracking.

Polyetherimide polymers and pre-polymers may have varying levels ofamine and anhydride end groups depending on the amounts of diamine anddianhydride used in the polymerization reaction and the degree ofcompleteness of the polymerization reaction. A variety of amine,anhydride, and anhydride derivatives such as carboxylic acids,carboxylate salts, amide-acids and amide-carboxylate salts are examplesof possible end groups. As used herein it will be understood that theterm “amine end groups” comprises end groups that are amines, and anyrelated end groups that are derived from amine end groups. As usedherein it will also be understood that the term “anhydride end groups”comprises end groups which are anhydrides and anhydride derivatives suchas carboxylic acid, carboxylate salts, amide-acids and amide-carboxylatesalts. All types, more than one type or essentially one type of theseend groups may be present. In general, total reactive end groupconcentrations of a polyetherimide can be 0.05 to 0.3 mole % resin. Incontrast, the total reactive end group concentrations of a pre-polymercan be 0.5 to 20 mole %. As used herein, the term “reactive end group”refers to any of the various possible end groups that can give rise tovolatile species during melt processing. Most reactive end groups willbe amine or anhydride. In one embodiment, the pre-polymer has a totalreactive end group content of 1 to 10 mole %, or, more specifically, 5to 10 mole %.

The concentration of amine, anhydride, and related end groups can beanalyzed by various titration and spectroscopic methods well known inthe art. Spectroscopic methods include infrared, nuclear magneticresonance, Raman spectroscopy, and fluorescence. Examples of infraredmethods are described in J. A. Kreuz, et al., and J. Poly. Sci. PartA-1, vol. 4, pp. 2067-2616 (1966). Examples of titration methods aredescribed in Y. J. Kim, et al., Macromolecules, vol. 26, pp. 1344-1358(1993). It may be advantageous to make derivatives of polymer end groupsto enhance measurement sensitivity using, for example, variations ofmethods as described in K. P. Chan et al., Macromolecules, vol. 27, p.6731 (1994) and J. S. Chao, Polymer Bull., vol. 17, p. 397 (1987).

The molecular weight of pre-polymer can be measured by gel permeationchromatography (GPC). The molecular weights as used here refer to theweight average molecular weight (Mw). In one embodiment, the pre-polymerhas a weight average molecular weight of 1,000 to 100,000 grams per mole(g/mole) as measured by gel permeation chromatography (GPC). In someembodiments the Mw can be 2,000 to 20,000.

The polymer comprises end groups reactive with anhydride, amine or acombination thereof under melt mixing conditions. Exemplary endgroupsinclude and are not limited to amine, anhydride, hydroxyl, alcohol,amide, epoxide, ester, thiol, acid and activated aromatic halide, andcombinations thereof. Exemplary polymers include polyimides,polyetherimides, polyamideimides, polyaryl ether ketones, polyarylketones, polyether ketones, polyether ether ketones, polyaryl sulfones,liquid crystal polymers, polyamides, polyesters, polysulfones,polyphenylene sulfides, polybenzimidazoles, polyphenylenes, andcombinations thereof. The foregoing exemplary polymers are commerciallyavailable e.g., Aurum polyimides (Mitsui), ULTEM polyetherimides (GE),PEEK (Victrex), Radel polysulfones (Solvay) and Fortron PPS (Ticona).

The polymer may be a polyetherimide derived from the dianhydrides anddiamines described above. In some embodiments the dianhydride(s) used inmaking the pre-polymer and/or polymer is selected from the groupconsisting of oxydiphthalic anhydride, bisphenol-A dianhydride, andcombinations thereof. In some embodiments the diamine(s) used in makingthe pre-polymer and/or polymer is selected from the group consisting ofdiamino diaryl sulfones, metaphenylene diamines, paraphenylene diaminesand combinations thereof. In some embodiments, the polymer is apolyetherimide comprising structural units derived from bisphenol-Adianhydride (BPADA) and diamino diarylsulfone (DAS). Bisphenol-Adianhydride has the following formula (XII):

Similar to the discussion above with regard to oxydiphthalic anhydride,the term “bisphenol-A dianhydride” is inclusive of chemical derivativesof the anhydride functionality which can function as a chemicalequivalent for the bisphenol-A dianhydride in polyetherimide formingreactions.

In one embodiment the diamino diaryl sulfone is diamino diphenylsulfone.

In one embodiment, the polymer is a BPADA/DAS polyetherimide comprisingmore than 1, or, specifically 10 to 1000, or, more specifically, 30 to500 structural units of the formula (XIII):

The polyetherimide can have a weight average molecular weight (Mw) of5,000 to 100,000 grams per mole (g/mole) as measured by gel permeationchromatography (GPC). In some embodiments the Mw can be 10,000 to80,000.

In some embodiments the polymer is a polyetherimide derived frombisphenol-A dianhydride (BPADA) and phenylene diamine (PD) (a BPADA/PDpolyetherimide). More specifically, the structural units can be derivedfrom bisphenol-A dianhydride (BPADA) and meta-phenylene diamine (MPD),BPADA and para-phenylene diamine (PPD), or combinations thereof.

Meta-phenylene diamine (MPD) has the following formula (IX):

Para-phenylene diamine (PPD) has the following formula (XI):

The BPADA/PD polyetherimide comprises more than 1, or, specifically 10to 1000, or, more specifically, 30 to 500 structural units of theformula (X), formula (XII) or a combination thereof:

In embodiments where the polymer is a polyetherimide, the polyetherimidemay be made using any suitable method known in the art. In oneembodiment, a method using a highly polar solvent that dissolves boththe reactant monomers and the resultant polymers can be used. Solventssuch as dimethyl formamide (DMF), dimethyl acetamide (DMAC), N-methylpyrrolidinone (NMP), hexamethyl phosphoramide (HMPA) and dimethylsulfoxide (DMSO) can be used in this method. The resultant polymers aretotally dissolved and can be isolated from solution by removal ofsolvent as part of a film casting or other evaporative process or byprecipitation using an anti-solvent such as methanol.

The compositions described herein may further contain fillers,reinforcements, additives, and combinations thereof. Exemplary fillersand reinforcements include fiber glass, milled glass, glass beads, flakeand the like. Minerals such as talc, wollastonite, mica, kaolin ormontinorillonite clay, silica, quartz, barite, and combinations of twoor more of the foregoing may be added. The compositions can compriseinorganic fillers, such as, for example, carbon fibers and nanotubes,metal fibers, metal powders, conductive carbon, and other additivesincluding nano-scale reinforcements as well as combinations of inorganicfillers.

Other additives include, UV absorbers; stabilizers such as lightstabilizers and others; lubricants; plasticizers; pigments; dyes;colorants; anti-static agents; foaming agents; blowing agents; metaldeactivators, and combinations comprising one or more of the foregoingadditives. Antioxidants can be compounds such as phosphites,phosphonites and hindered phenols or mixtures thereof. Phosphoruscontaining stabilizers including triaryl phosphite and aryl phosphonatesare of note as useful additives. Difunctional phosphorus containingcompounds can also be employed. Stabilizers may have a molecular weightgreater than or equal to 300. In some embodiments, phosphorus containingstabilizers with a molecular weight greater than or equal to 500 areuseful. Phosphorus containing stabilizers are typically present in thecomposition at 0.05-0.5% by weight of the formulation. Flow aids andmold release compounds are also contemplated.

In another embodiment, the compositions may further include secondpolymer. Examples of such polymers include and are not limited to PPSU(polyphenylene sulfone), PEI (poly(ether imide)), PSU (polysulfone), PC(polycarbonate), PPE (polyphenylene ether), PMMA (poly methylmethacrylate), ABS (acrylonitrile butadiene styrene), PS (polystyrene),PVC (polyvinylchloride), PFA (per fluoro aalkoxy alkane), MFA(co-polymer of TFE tetra fluoro ethylene and PFVE perfluorinated vinylether), FEP (Fluorinated ethylene propylene polymers), PPS(poly(phenylene sulfide), PEK (poly(ether ketone), PEEK(poly(ether-ether ketone), ECTFE (ethylene chloro trifluoro ethylene),PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PET(polyethylene terephthalate), POM (polyacetal), PA (polyamide), UHMW-PE(ultra high molecular weight polyethylene), PP (polypropylene), PE(polyethylene), HDPE (high density polyethylene), LDPE (low densitypolyethylene), PBI (polybenzimidizole), PAI (poly(amide-imide),poly(ether sulfone), poly(aryl sulfone), polyphenylenes,polybenzoxazoles, polybenzthiazoles, as well as blends and co-polymersthereof.

Compositions may be made by any suitable method. For instance,compositions can be made by melt mixing (compounding) the pre-polymer,the polymer and, optionally, additives, in a suitable device such astwin screw extruder at a suitable temperature, e.g., 250° C. to 450° C.Melt mixing is performed by mixing the composition components at atemperature sufficient to maintain the pre-polymer and the polymer in amolten state. The temperature is less than the degradation temperaturesof the pre-polymer and the polymer. In some embodiments an extruder isused for melt mixing. Optionally, the extruder may have a vacuum vent.In some embodiments the pre-polymer and the polymer are melt mixed toform the polymer blend and additional components are added to thepolymer blend. The polymer blend may be pelletized and then the polymerblend pellets melt mixed with additional components, or the additionalcomponents may be added to the polymer blend without a pelletizing step.

The pre-polymer may be present in an amount of 1 weight percent (wt %)to 99 wt %, or, more specifically, 10 wt % to 90 wt %, or, even morespecifically, 20 wt % to 80 wt %, based on the combined weight of thepre-polymer and the polymer. The polymer may be present in an amount of1 wt % to 99 wt %, or, more specifically, 10 wt % to 90 wt %, or, evenmore specifically, 20 wt % to 80 wt %, based on the combined weight ofthe pre-polymer and the polymer.

The compositions of the invention can be formed into articles by anynumber of methods. Preferred methods include, for example, injectionmolding, blow molding, compression molding, profile extrusion, sheet orfilm extrusion, sintering, gas assist molding, structural foam moldingand thermoforming. Film and sheet extrusion processes may include andare not limited to melt casting, blown film extrusion and calendering.Examples of such articles include, but are not limited to, films,membranes, tubing, composites, semi-conductor process tools, wirecoatings and jacketing, fluid handling components, cookware, foodservice items, medical devices, trays, plates, handles, helmets, animalcages, electrical connectors, enclosures for electrical equipment,engine parts, automotive engine parts, bearings, lighting sockets andreflectors, electric motor parts, power distribution equipment,communication equipment, computers and the like, including devices thathave molded in snap fit connectors. The blends can also be used asfibers. In addition the blends can be used as coatings, for examplepowder coatings.

Films may have a thickness of 0.1 to 1000 micrometers in some instances.Co-extrusion and lamination processes may be employed to form compositemulti-layer films or sheets. Single or multiple layers of coatings mayfurther be applied to the single or multi-layer substrates to impartadditional properties such as scratch resistance, ultra violet lightresistance, aesthetic appeal, etc. Coatings may be applied throughstandard application techniques such as rolling, spraying, dipping,brushing, or flow coating. Film and sheet may alternatively be preparedby casting a solution or suspension of the composition in a suitablesolvent onto a substrate, belt or roll followed by removal of thesolvent. Films may also be metallized using standard processes such assputtering, vacuum deposition and lamination with foil.

Oriented films may be prepared through blown film extrusion or bystretching cast or calendered films in the vicinity of the thermaldeformation temperature using conventional stretching techniques. Forinstance, a radial stretching pantograph may be employed for multi-axialsimultaneous stretching; an x-y direction stretching pantograph can beused to simultaneously or sequentially stretch in the planar x-ydirections. Equipment with sequential uniaxial stretching sections canalso be used to achieve uniaxial and biaxial stretching, such as amachine equipped with a section of differential speed rolls forstretching in the machine direction and a tenter frame section forstretching in the transverse direction

Compositions discussed herein may be converted to multiwall sheetcomprising a first sheet having a first side and a second side, whereinthe first sheet comprises a thermoplastic polymer, and wherein the firstside of the first sheet is disposed upon a first side of a plurality ofribs; and a second sheet having a first side and a second side, whereinthe second sheet comprises a thermoplastic polymer, wherein the firstside of the second sheet is disposed upon a second side of the pluralityof ribs, and wherein the first side of the plurality of ribs is opposedto the second side of the plurality of ribs.

The films and sheets described above may further be thermoplasticallyprocessed into shaped articles via forming and molding processesincluding but not limited to thermoforming, vacuum forming, pressureforming, injection molding and compression molding. Multi-layered shapedarticles may also be formed by injection molding a thermoplastic resinonto a single or multi-layer film or sheet substrate as described below:

1) Providing a single or multi-layer thermoplastic substrate havingoptionally one or more colors on the surface, for instance, using screenprinting of a transfer dye.

2) Conforming the substrate to a mold configuration such as by formingand trimming a substrate into a three dimensional shape and fitting thesubstrate into a mold having a surface which matches the threedimensional shape of the substrate.

3) Injecting a thermoplastic resin into the mold cavity behind thesubstrate to (i) produce a one-piece permanently bondedthree-dimensional product or (ii) transfer a pattern or aesthetic effectfrom a printed substrate to the injected resin and remove the printedsubstrate, thus imparting the aesthetic effect to the molded resin.

Those skilled in the art will also appreciate that common curing andsurface modification processes including and not limited toheat-setting, texturing, embossing, corona treatment, flame treatment,plasma treatment and vacuum deposition may further be applied to theabove articles to alter surface appearances and impart additionalfunctionalities to the articles. Accordingly, another embodiment of theinvention relates to articles, sheets and films prepared from thecompositions above.

The physical properties of the compositions, and articles derived fromthe compositions, are useful and can vary. For instance, in embodimentswhere the pre-polymer and the polymer comprise a common diamine, thepolymer blend can have a single resin glass trainsition temperature.

When the polymer blend has a single glass transition temperature, theglass transition temperature can be greater than or equal to 100° C.,or, more specifically, greater than or equal to 125° C., or, even morespecifically, greater than or equal to 150° C. The glass transitiontemperature can be less than or equal to 600° C.

In embodiments where the pre-polymer and the polymer do not have acommon monomer the compatible polymer blend has greater than one glasstransition temperature. In some embodiments the composition has twoglass transition temperatures. In some embodiments the lowest glasstransition temperature is greater than or equal to 50° C., or, morespecifically, greater than or equal to 75° C., or, even morespecifically, greater than or equal to 100° C. The lowest glasstransition temperature can be less than or equal to 600° C.

In some embodiments the polymer blend has a melt viscosity of 50 to20,000 Pascal-seconds at 380° C. as measured by ASTM method D3835 usinga capillary rheometer with a shear rate of 100 to 10,000 1/sec. Withinthis range the melt viscosity can be greater than or equal to 100, or,more specifically, greater than or equal to 200. Also within this rangethe melt viscosity can be less than or equal to 15,000, or, morespecifically, less than or equal to 10,000 Pascal-seconds.

In another embodiment, the composition (and articles made from thecomposition) can have heat deflection temperature (HDT) of greater thanor equal to 100° C., according to ASTM D648. In one embodiment,compositions can have an HDT ranging of 100° C. to 400° C., according toASTM D648. In another embodiment, the compositions, and articles derivedfrom the compositions, can have a tensile strength of greater than orequal to 70 megaPascals (MPa) according to ASTM D638. In one embodiment,the compositions and articles can have a tensile strength of 70 MPa to500 MPa. The coefficient of thermal expansion of the compositions canvary. In one embodiment, the coefficient of thermal expansion is lessthan 100 ppm/° C. from 30° C.-200° C. as measured by thermal mechanicalanalysis with a thermal ramp rate of 5° C./minute. In anotherembodiment, the coefficient of thermal expansion is 5 to 100 ppm/° C.from 30° C.-200° C. as measured by thermal mechanical analysis with athermal ramp rate of 5° C./minute.

Compositions and articles derived from the compositions can also exhibitadvantageous heat aging performance properties. For instance, in oneembodiment, a composition (and articles derived from the composition)can have a continuous use temperature of greater than or equal to 150°C., or above. A composition can have a continuous use temperature of150° C. to 400° C.

Advantageously, the compositions described herein now provide previouslyunavailable compositions and articles. For instance, the compositionscan overcome the problem of delamination in an immiscible, incompatibleblends and exhibit immiscible, but compatible blend features havinghighly useful applications. The compositions can provide a much widerrange of miscible blend compositions. Compositions of the invention canexhibit an improved visual transparent appearance. Extending the rangeof miscibility in such blends has significant practical importance. Itis now possible to make a wide variety of blend compositions with asingle glass transition temperature (Tg) and predetermined transparency.

The following examples are included to provide additional guidance tothose skilled in the art. The examples provided are merelyrepresentative and are not intended to limit the invention, as definedin the appended claims, in any manner.

EXAMPLES

Materials used in the Examples are listed Table 1. Amounts listed in theExamples are in weight percent based on the combined weight of the firstand second polymers used.

TABLE 1 PEI 1 (ODPA/DAS) A polyetherimide comprising structural unitsderived from oxydiphthalic anhydride and diamino diphenyl sulfone andhaving a molecular weight of 30,000 g/mol. PEI 2 (BPADA/DDS) Apolyetherimide comprising structural units derived from bisphenol-Adianhydride and diamino diphenyl sulfone and having a molecular weightof 38,000 g/mol. This polymer is commercially available from GE Plasticsunder the tradename ULTEM XH6050. PEI 3 (BPADA/MPD) A polyetherimidecomprising structural units derived from bisphenol-A dianhydride andmeta-phenylene diamine and having a molecular weight of 38,000 g/mol.This polymer is commercially available from GE Plastics under thetradename ULTEM 1000. Pre-Polymer A polyetherimide comprising structural(ODPA/DAS) units derived from oxydiphthalic anhydride and diaminodiphenyl sulfone, having a weight average molecular weight of 15,000g/mol and a total reactive end group content of 14 mole %.

Examples 1-9

The purpose of these examples is to show that blending with a reactivepre-polymer can overcome the problem of delamination in an immiscible,incompatible blend. These examples also show that blending with areactive pre-polymer can improve the miscibility in an immiscible, butcompatible blend and result in a much wider range of miscible blendcompositions. The examples also show how visual appearance can alsoimprove.

Preparation Techniques

The compositions shown in Table 2 were prepared by melt mixing thecomponents in a twin screw extruder at temperatures of 300° C. to 430°C. with vacuum venting. The screw speed typically varied from 100 to 350rotations per minute (RPM).

Testing Techniques

The compositions were tested for glass transition temperature usingdifferential scanning calorimetry (DSC). Morphology was determined byvisual inspection using ASTM tensile bars. The tensile bars were aged at280° C. for 240 hours and checked for delamination by visual inspection.Visual inspection was determined by normal vision (e.g., 20/20 vision inthe absence of any magnifying device with the exception of correctivelenses necessary for normal eyesight) at a distance of one half (½)meter. Results are shown in Tables 2 and 3.

Results

TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4* Pre-Polymer 85 75 60 — (ODPA/DDS) PEI 1— — — 85 (ODPA/DDS) PEI 3 15 25 40 15 (BPADA/ MPD) T_(g)  2  2  2  2Morphology Two-Phase Two-Phase Two-Phase Two-Phase Appearance OpaqueOpaque Opaque Opaque Delamination No No No Yes on Heat Aging*Comparative example

TABLE 3 Ex. 5 Ex. 6 Ex. 7 Ex. 8* Ex. 9* Pre-Polymer 85 75 60 — —(ODPA/DDS) PEI 1 — — — 85 60 (ODPA/DDS) PEI 2 15 25 40 15 40 (BPADA/DDS)T_(g)  1  1  1  2  2 Morphology One-Phase One-Phase One-Phase Two-PhaseTwo-Phase Appearance Transparent Transparent Transparent TranslucentTranslucent Delamination No No No No No on Heat Aging *Comparativeexamples

Discussion

Examples 1-3 (which are based on pre-polymers) when compared toComparative Example 4 (which is not based on a pre-polymer) show theunexpected behavior of polyetherimide blends when a pre-polymer was usedto make the blends. Blends of PEI 1 and PEI 3 exhibited two phasemorphology and delamination even at low levels of PEI 3 (15 weight %).In contrast, despite the two phase resin morphology, blends ofpre-polymer and PEI 3, even at 40 weight %, did not not showdelamination after heat aging at 280° C. for 240 hours. Surprisingly,melt mixing with a reactive pre-polymer overcame the problem ofdelamination in an immiscible, incompatible blend and resulted in animmiscible, but compatible blend of practical importance.

Examples 5-7 (which are based on pre-polymers) when compared toComparative Examples 8 and 9 (which are not based on pre-polymers)illustrated the unexpected behavior of polyetherimide blends when apre-polymer was used to make the blends. Blends of PEI 1 and PEI 2showed two phase morphology at low levels of PEI 2 (15 weight %).Despite the multiphasic resin morphology, the blends of PEI 1 and PEI 2did not show any delamination. In contrast, blends of pre-polymer andPEI 2 showed a monophasic morphology with a single Tg at the same levelsof PEI 2 (15 weight %) and even at a high level of PEI 2 (40 weight %).No delamination after heat aging at 280° C. for 240 hours was observedin any of these blends.

The blend of Example 7 also demonstrated excellent properties. Moreparticularly, the blend of Example 7 exhibited tensile strength of 120MPa, flexural strength of 170 MPa, HDT of 240° C. under a load of 1.8MPa, and a coefficient of thermal expansion of 45 ppm/° C. from 30-200°C.

Thus, Examples 5-7 showed that blending with a reactive pre-polymerimproved the miscibility in an immiscible, but compatible blend andresulted in a much wider range of miscible blend compositions. Thevisual appearance also improved from transluscent to transparent.Extending the range of miscibility in such a blend has significantpractical importance since a wide variety of blend compositions with asingle Tg and transparency could now be designed.

While the invention has been described with reference to severalembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing fromessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiments disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims. All patents identified by number herein are incorporated byreference in their entirety.

1. A method of making a polymer blend comprising: melt mixing (a) apre-polymer having a component selected from the group consisting offree amine groups, free anhydride groups, and combinations thereof andcomprising structural units derived from a dianhydride and a diamine,and (b) a polymer comprising a reactive member selected from the groupconsisting of structural groups, end groups, and combinations thereof,wherein the reactive member is reactive with the free anhydride groups,the free amine groups, or combinations thereof and wherein the polymerblend is non-delaminated.
 2. The method of claim 1, wherein thedianhydride is oxydiphthalic anhydride and the diamine is a diaminodiaryl sulfone.
 3. The method of claim 1, wherein the polymer isselected from the group consisting of polyimides, polyetherimides,polyamideimides, polyaryl ether ketones, polyaryl ketones, polyetherketones, polyether ether ketones, polyaryl sulfones, liquid crystalpolymers, polyamides, polyesters, polysulfones, polyphenylene sulfides,polybenzimidazoles, polyphenylenes, and combinations of two or more ofthe foregoing.
 4. The method of claim 1, wherein the pre-polymer ispresent in an amount of 1 weight percent to 99 weight percent, based onthe combined weight of the pre-polymer and the polymer and the polymeris present in an amount of 1 weight percent to 99 weight percent, basedon the combined weight of the pre-polymer and the polymer.
 5. The methodof claim 4, wherein the pre-polymer is present in an amount of 10 weightpercent to 90 weight percent, based on the combined weight of thepre-polymer and the polymer and the polymer is present in an amount of10 weight percent to 90 weight percent, based on the combined weight ofthe pre-polymer and the polymer.
 6. The method of claim 5, wherein thepre-polymer is present in an amount of 20 weight percent to 80 weightpercent, based on the combined weight of the pre-polymer and the polymerand the polymer is present in an amount of 20 weight percent to 80weight percent, based on the combined weight of the pre-polymer and thepolymer.
 7. The method of claim 1, wherein the pre-polymer has a ratioof carbon atoms/(nitrogen atoms+oxygen atoms+sulfur atoms) of 2.8 to4.2.
 8. A method of making a polymer blend comprising: melt mixing (a) apre-polymer comprising a component selected from the group consisting offree amine groups, free anhydride groups, and combinations thereof andfurther comprising structural units derived from a first dianhydride anda first diamine; (b) a polymer comprising a reactive member selectedfrom the group consisting of structural groups, end groups, andcombinations thereof and further comprising structural units derivedfrom a second dianhydride and a second diamine; wherein the firstdianhydride is the same as the second dianhydride or the first diamineis the same as the second diamine.
 9. The method of claim 8, wherein thefirst dianhydride or the second anhydride is selected from the groupconsisting of oxydiphthalic anhydrides, bisphenol-A dianhydrides, andcombinations thereof.
 10. The method of claim 8, wherein the firstdiamine or the second diamine is selected from the group consisting ofdiamino diaryl sulfones, metaphenylene diamines, paraphenylene diamines,and combinations thereof.
 11. The method of claim 8, wherein thepre-polymer is present in an amount of 1 weight percent to 99 weightpercent, based on the combined weight of the pre-polymer and the polymerand the polymer is present in an amount of 1 weight percent to 99 weightpercent, based on the combined weight of the pre-polymer and thepolymer.
 12. The method of claim 8, wherein the pre-polymer is presentin an amount of 10 weight percent to 90 weight percent, based on thecombined weight of the pre-polymer and the polymer and the polymer ispresent in an amount of 10 weight percent to 90 weight percent, based onthe combined weight of the pre-polymer and the polymer.
 13. The methodof claim 8, wherein the pre-polymer is present in an amount of 20 weightpercent to 80 weight percent, based on the combined weight of thepre-polymer and the polymer and the polymer is present in an amount of20 weight percent to 80 weight percent, based on the combined weight ofthe pre-polymer and the polymer.
 14. The method of claim 8, wherein thepre-polymer comprises structural units derived from oxydiphthalicanhydrides and diamino diaryl sulfones and the polymer comprisesstructural units derived from bisphenol-A dianhydrides and diaminodiaryl sulfones.
 15. The composition of claim 8, wherein the pre-polymerhas a ratio of carbon atoms/(nitrogen atoms+oxygen atoms+sulfur atoms)of 2.8 to 4.2.
 16. A method of making a polymer blend comprising: meltmixing (a) a pre-polymer comprising a component selected from the groupconsisting of free amine groups, free anhydride groups, and combinationsthereof and further comprising structural units derived from a firstdianhydride and a first diamine; (b) a polymer comprising a reactivemember selected from the group consisting of structural groups, endgroups, and combinations thereof and further comprising structural unitsderived from a second dianhydride and a second diamine; and wherein thefirst dianhydride is different from the second dianhydride and the firstdiamine is different from the second diamine.
 17. The method of claim16, wherein the first dianhydride or the second anhydride is selectedfrom the group consisting of oxydiphthalic anhydrides, bisphenol-Adianhydrides, and combinations thereof.
 18. The method of claim 16,wherein the first diamine or the second diamine is selected from thegroup consisting of diamino diaryl sulfones, metaphenylene diamines,paraphenylene diamines, and combinations thereof.
 19. The method ofclaim 16, wherein the pre-polymer is present in an amount of 1 weightpercent to 99 weight percent, based on the combined weight of thepre-polymer and the polymer and the polymer is present in an amount of 1weight percent to 99 weight percent, based on the combined weight of thepre-polymer and the polymer.
 20. The method of claim 16, wherein thepre-polymer is present in an amount of 10 weight percent to 90 weightpercent, based on the combined weight of the pre-polymer and the polymerand the polymer is present in an amount of 10 weight percent to 90weight percent, based on the combined weight of the pre-polymer and thepolymer.
 21. The method of claim 16, wherein the pre-polymer is presentin an amount of 20 weight percent to 80 weight percent, based on thecombined weight of the pre-polymer and the polymer and the polymer ispresent in an amount of 20 weight percent to 80 weight percent, based onthe combined weight of the pre-polymer and the polymer.
 22. The methodof claim 16, wherein the pre-polymer has a ratio of carbonatoms/(nitrogen atoms+oxygen atoms+sulfur atoms) of 2.8 to 4.2.
 23. Amethod of making a polyimide polymer blend having a predetermined glasstransition temperature comprising: selecting a glass transitiontemperature for the blend; and melt mixing a pre-polymer and a polymer,wherein the pre-polymer and polymer are present in amounts sufficient toprovide a blend having the selected glass transition temperature,wherein the pre-polymer comprises a component selected from the groupconsisting of free amine groups, free anhydride groups, and combinationsthereof and further comprises structural units derived from a firstdianhydride and a first diamine, wherein the polymer comprises areactive member selected from the group consisting of structural groups,end groups, and combinations thereof, and the reactive member isreactive with the free anhydride groups, the free amine groups, orcombinations thereof, wherein the polymer comprises structural unitsderived from a second dianhydride and a second diamine, and wherein thefirst dianhydride is the same as the second dianhydride or the firstdiamine is the same as the second diamine.
 24. The method of claim 23,wherein the pre-polymer has a ratio of carbon atoms/(nitrogenatoms+oxygen atoms+sulfur atoms) of 2.8 to 4.2.
 25. A method of making apolyimide polymer blend having a greater than one predetermined glasstransition temperatures comprising: selecting the glass transitiontemperatures for the blend; and melt mixing a pre-polymer and a polymer,wherein the prepolymer comprises a component selected from the groupconsisting of free amine groups, free anhydride groups, and combinationsthereof and further comprises structural units derived from a firstdianhydride and a first diamine, wherein the polymer comprises areactive member selected from the group consisting of structural groups,end groups, and combinations thereof, and the reactive member isreactive with the free anhydride groups, the free amine groups, orcombinations thereof, wherein the polymer comprises structural unitsderived from a second dianhydride and a second diamine, and wherein thefirst dianhydride is different from the second dianhydride and the firstdiamine is different from the second diamine.
 26. The method of claim25, wherein the pre-polymer has a ratio of carbon atoms/(nitrogenatoms+oxygen atoms+sulfur atoms) of 2.8 to 4.2.
 27. A method of making acomposition comprising: forming a polymer blend melt mixing (a) apre-polymer having a component selected from the group consisting offree amine groups, free anhydride groups, and combinations thereof andcomprising structural units derived from a dianhydride and a diamine,and (b) a polymer comprising a reactive member selected from the groupconsisting of structural groups, end groups, and combinations thereof,wherein the reactive member is reactive with the free anhydride groups,the free amine groups, or combinations thereof and wherein the polymerblend is non-delaminated, and melt mixing the polymer blend with anadditional component.
 28. The method of claim 27, wherein the additionalcomponent comprises a second polymer.
 29. The method of claim 27,wherein the second polymer is selected from the group consisting ofpolyphenylene sulfone, polyetherimide, polysulfone, polycarbonate,polyphenylene ether, poly methyl methacrylate, acrylonitrile butadienestyrene, polystyrene, polyvinylchloride, perfluoroalkoxyalkane polymer,co-polymer of tetra fluoro ethylene and perfluorinated vinyl ether,fluorinated ethylene propylene polymer, poly(phenylene sulfide,poly(ether ketone), poly(ether-ether ketone), ethylene chloro trifluoroethylene polymer, polyvinylidene fluoride, polytetrafluoroethylene,polyethylene terephthalate, polyacetal, polyamide, ultra high molecularweight polyethylene, polypropylene, polyethylene, high densitypolyethylene, low density polyethylene, polybenzimidizole,poly(amide-imide), poly(ether sulfone), poly(aryl sulfone),polyphenylenes, polybenzoxazoles, polybenzthiazoles and blends andco-polymers thereof.
 30. The method of claim 27, wherein the additionalcomponent comprises a filler, reinforcement, additive or combinationthereof.
 31. The method of claim 27, wherein the pre-polymer has a ratioof carbon atoms/(nitrogen atoms+oxygen atoms+sulfur atoms) of 2.8 to4.2.